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• A chemical sample consists of particles (atoms, ions, or molecules) that are in constant
random motion at various speeds, rebounding elastically from collisions with each other.
The average kinetic energy of the particles is perceived as the temperature of the sample.
• An effective collision requires sufficient energy and correct orientation (positioning) of the
colliding particles so that bonds can be broken and new bonds formed.
• Ineffective collisions involve particles that rebound from the collision, essentially unchanged
in nature.
• The rate of a given reaction depends on two factors related to collisions: the frequency of
collisions and the fraction of those collisions that are effective.
• A minimum activation energy (the energy of the activated complex) is required for a collision
between particles to be effective, that is, energetic enough to cause the breaking and
forming of bonds to product new particle structures
• The rate of any reaction depends on the nature of the chemical substances reacting
because both the strength of bond(s) to be broken and the location of the bond(s) in the
particle structure affect the likelihood that any given collision is effective.
• An increase in temperature increases the rate of a reaction for two reasons. The total
number of collisions possible per unit time is increased slightly, but more importantly, the
fraction of collisions which are energetic enough to be effective is increased dramatically.
Temperature – Temp , Rate (and vice-versa)
2. Reaction Rate or Rate of Reaction: change in amounts of reactants or products over time.
3. Rate-Determining Step: the slowest reaction step in any reaction mechanism. It has a fairly
high “activation energy” and the rate of the overall reaction is controlled by this step.
Endothermic Reaction
Endothermic reactions are always positive.
Things to Remember:
• Always start at zero.
• Endothermic = +
• Exothermic = -
• Label the diagram!
Eact(fwd) = 134 Kj
∆H = -226 Kj
* Eact(rev) = ? (360 Kj)
* ∆H = + 226 Kj
F (s) is the reaction intermediate. It is a product in the first step, it becomes a reactant in the
second step, and it is not present in the overall formula.
Things to Remember:
• The activation energy decreases and the ∆H remains the same when a catalyst is added to
a reaction.
• A catalyst changes the activation energy of the reaction.
2A + B2 D + E
Step 1 : A + B2 AB2
Step 2 : AB2 + C AB2C
Step 3 : AB2C + A A2B2 + C
Step 4 : A2B2 D + E
2. Homogenous Equilibrium: reactants and products are in the same phase (state of matter –
solid, liquid, gas).
1. Equilibrium is achieved in a reversible process when the rates of opposing changes are
equal.
3. Equilibrium can only be achieved in a closed system – does not allow anything to escape or
enter.
4. Equilibrium can be approached from either direction (left to right, or, right to left).
[ R ]c [ S ]d products
Kc =
[ P ]a [ Q ]b reactants
Where “Kc” is the equilibrium at constant, “a, b, c, d” are the coefficients of “P, Q, R, S”, and [ ]
is the concentration in mols/litre.
Things to Remember:
• When solving for “Kc”, you do not have to use units, for instance: mol, litres, or mol/l.
• If a problem states “mol”, then you must divide the numbers of mol by the litres to obtain
“mol/l”.
• Pure liquids and solids are not included (this is in relation to the subscript of each chemical
compound, (l) and (s)).
• If the coefficient (either a, b, c, d) is 1, do not write it as a superscript number in the general
equilibrium reaction formula, as it is understood to already be there.
• If there is only 1 product or reactant when calculating “Kc”, replace with a 1.
• If a problem states that products or reactants are initially a number, do not use these
numbers when determining “Kc” or a product or reactant; you must only use numbers when
it states that they are at “equilibrium”.
[ R ]c [ S ]d
Kc =
[ P ]a [ Q ]b
2. A mixture of nitrogen and chlorine gases was kept at a certain temperature in a 5.0 litre
reaction flask. When the equilibrium mixture was analyzed, it was found to contain 0.0070 mol of
N2 (g), 0.0022 mol of Cl2 (g), and 0.95 mole of NCL3 (g). Calculate the equilibrium constant for
this reaction.
[ NCl3 (g) ]2
Kc =
[ N2 (g) ] [ Cl2 (g) ]3
(0.19) 2
Kc =
(0.0014)(0.00044) 3
0.036
Kc =
(1.19 x 10 -13)
Things to Remember:
• If “energy” or “kj” is stated on the left side (reactants), it is considered to be endothermic;
however, if it is stated on the right side (products), it is considered to be exothermic.
Temperature:
The container is heated.
H2O (l) + energy H2O (g)
Effect: shift right
Energy is removed.
2SO2 (g) + O2 (g) 2SO3 (g) + energy
Effect: shift right
Problem:
The following reaction has an equilibrium constant of 25.0 at 1100 K.
2.00 mol of H2 (g) and 3.00 mol of I2 (g) are placed in a 1.00 litre reaction vessel at 1100 K.
What is the equilibrium concentration of each gas?
What is Required?
You need to find [ H2 (g) ], [ I2 (g) ], and [ HI (g) ].
What is Given?
You have the balanced chemical equation. You know the equilibrium constant for this reaction,
Kc = 25.0. You also know the concentrations of the reactants and product: [ H2 (g) ]i = 2.00
mol/l, [ I2 (g) ]i = 3.00 mol/l, and [ HI (g) ]i = 0.
Step 1: Set up an ICE table. Let the change in molar concentrations of the reactants be x. Use
the stoichiometry of the chemical equation to write expressions for the equilibrium
concentrations. Record these expressions in your ICE table.
Step 2: Write the equilibrium expression. Substitute the expressions for the equilibrium
concentrations into the equilibrium expression. Rearrange the equilibrium expression into the
form of a quadratic equation. Solve the quadratic equation for x.
Step 3: Substitute x into the equilibrium line of the ICE table to find the equilibrium
concentrations.
Change -x -x +2x
[ HI (g) ]2
Kc =
[ H2 (g) ] [ I2 (g) ]
(2x) 2
25.0 =
(2.00 – x)(3.00 – x)
(2X)2
25.0 =
(6.00 – 2.00 x -3.00x + x2)
This equation does not involve a perfect square. It must be re-arranged into a quadratic
equation.
4x2
25.0 =
(6.00 – 5.00x + x2)
-b + √b22 – 4ac
x=
2a
[ H2 (g) ] = 2.00 – x
[ H2 (g) ] = 2.00 – 1.7
[ H2 (g) ] = 0.3 mol/l
[ I2 (g) ] = 3.00 – x
[ I2 (g) ] = 3.00 – 1.7
[ I2 (g) ] = 1.3 mol/l
[ HI (g) ] = 2x
[ HI (g) ] = 2(1.7)
[ HI (g) ] = 3.4 mol/l
(3.4)2
25.0 =
(0.3)(1.3)
(3.4)2
25.0 =
0.39
11.56
25.0 =
0.39
25.0 = 29.64
Problem:
The following reaction increases the proportion of hydrogen gas for use as a fuel.
This reaction has been studied at different temperatures to find the optimum conditions. At 700
K, the equilibrium constant is 8.3. Suppose that you start with 1.0 mol of CO (g) and 1.0 mol of
H2O (g) in a 5.0 litre container. What amount of each substance will be present in the container
when the gases are at equilibrium, at 700 K?
What is Required?
You need to find the amount (in mols) of CO (g), H2O (g), H2 (g), and CO2 (g) at equilibrium.
What is Given?
You have the balanced chemical equation. You know the initial amount of each gas, the volume
of the container, and the equilibrium constant.
Step 2: Set up an ICE (initial, change, and equilibrium) table. Record the initial concentrations
you calculated in step 1 in your ICE table. Let the change in molar concentrations of the
reactants be x. Use the stoichiometry of the chemical equation to write the record expressions
for the equilibrium concentrations.
Change -x -x +x +x
(x)(x)
8.3 =
(0.2 – x)(0.2 – x)
(X)2
8.3 =
(0.2 – x)2
√ (X)2
√8.3 =
√ (0.2 – x)2
(x)
+ 2.88 =
(0.2 – x)
+ 2.88 (0.2 - x) =x
+ 2.88 (0.2 - x) =x
0.148 =x
0.306 =x
Step 4: The value x = 0.306 is physically impossible because it would result in a negative
concentration of both CO (g) and H2O (g) at equilibrium.
Therefore:
[ CO (g) ] = 0.20 – x
[ CO (g) ] = 0.20 – 0.148
[ CO (g) ] = 0.052
To find the amount of each gas, multiply the concentrations of each gas by the volume of the
container (5.0 litre in this case).
(0.75)2
8.3 =
(0.25)2
Things to Remember:
• “x” will always be negative on the reactant side, while “x” will always be positive on the
product side.
• Be sure to use the coefficient on the chemical compound. For example: 2HI(g).
In a 1.0 litre container, the chemist added 1.7 x 10-1 mol of SO2 (g) to 1.1 x 10-1 mol of NO2 (g).
At equilibrium, the concentration of SO3 (g) was found to be 0.089 mol/l. What is the value of
“Kc” for the reaction at this temperature?
[ SO2 (g)]i = 1.7 x 10-1 mol ÷ 1.0 l = 1.7 x 10-1 mol mol/l
[ NO2 (g)]i = 1.1 x 10-1 mol ÷ 1.0 l = 1.1 x 10-1 mol/l
(0.089)(0.089)
Kc =
(0.081)(0.021)
0.007921
Kc =
0.001701
Kc = 4.7 (rounded)